Dyes, a process for their preparation and their use

ABSTRACT

Dyes of the formula                    
     in which Me, R 1 , X 1 , A, u and q are as defined in the specification are particularly suitable for dyeing cotton and produce dyeings with good all-round properties.

The present invention relates to novel dyes, in particular reactivedyes, a process for their preparation and their use for dyeing orprinting textile fibre materials.

The practice of dyeing using reactive dyes has recently led to increasedrequirements regarding the quality of the dyeings and the profitabilityof the dyeing process. There consequently continues to be a need fornovel reactive dyes which have improved properties in particular inrespect of application.

Reactive dyes which have an adequate substantivity and at the same timea good ease of washing off for the unfixed portions are requirednowadays for dyeing. They should furthermore have a good tinctorialyield and a high reactivity, and in particular dyeings with high degreesof fixing should be produced. These requirements are not met in allproperties by the known dyes.

The present invention is therefore based on the object of discoveringnovel improved dyes, in particular reactive dyes, which are used fordyeing and printing fibre materials and have the qualities characterizedabove to a high degree. The novel dyes should have the distinctivefeatures in particular of high fixing yields and high fibre-dye bondstabilities, and furthermore the portions not fixed to the fibre shouldbe easy to wash out. They should furthermore produce dyeings with goodall-round properties, for example light- and wetfastness properties.

It has been found that the object described is substantially achievedwith the novel dyes defined below.

The present invention therefore relates to dyes of the formula (1)

in which

Me is Cu or Ni,

R₁ is hydrogen or substituted or unsubstituted C₁-C₄alkyl or R₁ is asdefined for A,

X₁ is halogen, hydroxyl, C₁-C₄alkoxy, substituted or unsubstitutedC₁-C₄alkylthio or amino or

is an N-heterocyclic radical which may contain further heteroatoms,

u is the number 1, 2, 3 or 4,

q is the number 0 or 1,

the benzene rings I, II or III are unsubstituted or further substitutedand

A is a radical of the formula (2a), (2b) or (3)

in which

B₁ and B₂ independently of one another are an aliphatic bridge member,

D₁ and D₂ independently of one another are the radical of a diazocomponent of the benzene or naphthalene series,

R₂ is hydrogen or substituted or unsubstituted C₁-C₄alkyl,

R₃ and R₆ independently of one another are hydrogen, cyano, carbamoyl orsulfomethyl,

R₄ is hydrogen, C₁-C₄alkyl or amino,

R₅ is amino or N-mono- or N,N—di—C₁-C₄alkylamino which are unsubstitutedor substituted in the alkyl moiety and

R₇ is hydrogen or C₁-C₄alkyl.

The dyes of the formula (1) contain at least two, preferably 2 to 6, andin particular 2 to 4 sulfo groups, each of which is either in the formof its free acid or, preferably, salts thereof. Salts are, for example,the alkali metal, alkaline earth metal or sodium salts, salts of anorganic amine or mixtures thereof. Examples are sodium, lithium,potassium or ammonium salts, the salt of mono-, di- or triethanolamineor Na/Li- or Na/Li/NH₄ mixed salts.

Me is preferably Cu.

Substituted or unsubstituted C₁-C₄alkyl R₁ and R₂ can be methyl, ethyl,n- or i-propyl or n-, sec-, tert- or isobutyl which are unsubstituted orsubstituted, for example by hydroxyl, sulfo, sulfato, carboxyl, cyano,halogen, C₁-C₄alkoxycarbonyl or carbamoyl, in particular by hydroxyl,sulfo, sulfato or carboxyl.

R₁ is preferably hydrogen, C₁-C₄alkyl which is unsubstituted orsubstituted by hydroxyl, or a radical A, particularly preferablyhydrogen, methyl, ethyl or β-hydroxyethyl or a radical A, and especiallypreferably hydrogen or a radical A.

Halogen X₁ is, for example, fluorine, chlorine or bromine.

C₁-C₄alkoxy X₁, is, for example, methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy or isobutoxy, preferably methoxy or ethoxy, and in particularmethoxy.

C₁-C₄alkylthio X₁ is, for example, methylthio, ethylthio, n-propylthio,isopropylthio or n-butylthio, in particular ethylthio or n-propylthio.The radicals mentioned are unsubstituted or substituted in the alkylmoiety by hydroxyl, carboxyl or sulfo. The substituted radicals arepreferred.

Substituted or unsubstituted amino X₁ is amino which is unsubstituted orsubstituted on the N atom, for example the following radicals:

N-mono- or N,N- di- C₁-C₄alkylamino, which includes both theunsubstituted radicals and the radicals substituted in the alkyl moiety,for example by C₁-C₄-alkoxy, hydroxyl, carboxyl, sulfo or sulfato; theradicals substituted in the alkyl moiety are preferred;

C₅-C₇-cycloalkylamino, which includes both the unsubstituted radicals,and the radicals substituted in the cycloalkyl ring, for example byC₁-C₄alkyl, in particular methyl; the corresponding cyclohexyl radicalsare preferred such radicals;

phenylamino or N—C₁-C₄-alkyl-N-phenylamino, which includes both theunsubstituted radicals and the radicals substituted in the phenyl ring,for example by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyl or sulfo;these radicals are preferably unsubstituted in the phenyl ring orsubstituted by sulfo.

N-heterocyclic radicals X₁ which may contain further heteroatoms are,for example, morpholino or piperidin-1-yl.

X₁ is preferably fluorine or chlorine.

u is preferably the number 1, 2 or 3, in particular 2 or 3.

q is preferably the number 1.

Aliphatic bridge members B₁ and B₂ are, independently of one another,for example, straight-chain or branched C₂-C₁₂alkylene which isunsubstituted or substituted by hydroxyl, C₁-C₄alkoxy, sulfato or sulfoand/or interrupted once or several times by —O— or —NR′—, in which R′ ishydrogen or C₁-C₄alkyl, preferably hydrogen, methyl or ethyl, andparticularly preferably hydrogen. B₁ and B₂ independently of one anotherare preferably straight-chain or branched C₂-C₆alkylene, which isunsubstituted or substituted by hydroxyl, sulfo or sulfato, andparticularly preferably unsubstituted straight-chain or branchedC₂-C₆-alkylene. Examples of particularly preferred radicals B₁ and B₂are 1,2-ethylene, 1,3-propylene, 2-hydroxy-1,3-propylene, 1,4-butylene,2-methyl-1,5-pentylene and 1,6-hexylene, in particular 1,2-propylene and1,2-ethylene, and especially 1,2-ethylene.

Substituents which are customary in dyes are suitable for D₁ and D₂.Examples are the following: C₁-C₄alkyl, which is to be understood asmeaning methyl, ethyl, n- or isopropyl or n-, iso-, sec- or tert-butyl;C₁-C₄alkoxy, which is to be understood as meaning methoxy, ethoxy, n- orisopropoxy or n-, iso-, sec- or tert-butoxy; hydroxy-C₁-C₄alkoxy;phenoxy; C₂-C₆alkanoylamino which is unsubstituted or substituted in thealkyl moiety by hydroxyl or C₁-C₄alkoxy, for example acetylamino,hydroxyacetylamino, methoxyacetylamino or propionylamino; benzoylaminowhich is unsubstituted or substituted in the phenyl moiety by hydroxyl,sulfo, halogen, C₁-C₄alkyl or C₁-C₄alkoxy; C₁-C₆alkoxycarbonylaminowhich is unsubstituted or substituted in the alkyl moiety by hydroxyl,C₁-C₄alkyl or C₁-C₄-alkoxy; phenoxycarbonylamino; which is unsubstitutedor substituted in the phenyl moiety by hydroxyl, C₁-C₄alkyl orC₁-C₄alkoxy; amino; N—C₁-C₄alkyl- or N,N- di- C₁-C₄alkylamino which areunsubstituted or substituted in the alkyl moiety by hydroxyl,C₁-C₄alkoxy, carboxyl, cyano, halogen, sulfo, sulfato, phenyl orsulfophenyl, for example methylamino, ethylamino, N,N-dimethylamino,N,N-diethylamino, β-cyanoethylamino, β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, β-sulfoethylamino, γ-sulfo-n-propylamino,β-sulfatoethylamino, N-(3-sulfobenzyl)amino orN-ethyl-N-(3-sulfobenzyl)amino, N-(β-sulfoethyl)-N-benzylamino;cyclohexylamino; N-phenylamino or N—C₁-C₄alkyl-N-phenylamino which areunsubstituted or substituted in the phenyl moiety by nitro, C₁-C₄alkyl,C₁-C₄alkoxy, carboxyl, halogen or sulfo; C₁-C₄alkoxycarbonyl, forexample methoxy- or ethoxycarbonyl; trifluoromethyl; nitro; cyano;halogen, which is to be understood generally as meaning, for example,fluorine, bromine or, in particular chlorine; ureido, hydroxyl,carboxyl, sulfo; sulfomethyl; carbamoyl; N—C₁-C₄alkylcarbamoyl, forexample N-methylcarbamoyl or N-ethylcarbamoyl; carbamido; sulfamoyl;N—C₁-C₄alkylsulfamoyl, for example N-methylsulfamoyl orN-ethylsulfamoyl; N-phenylsulfamoyl or N—C₁-C₄alkyl-N-phenylsulfamoyl;which are unsubstituted or substituted in the phenyl moiety by sulfo orcarboxyl; and C₁-C₄alkylsulfonyl, for example methyl- or ethylsulfonyl;

which, with the exception of sulfo, are also further substituents in thebenzene rings II, II or III.

Further substituents in the benzene rings I, II or III are preferablymethyl, ethyl, methoxy, ethoxy, acetylamino, benzylamino, amino,chlorine, bromine, ureido, hydroxyl, carboxyl or sulfomethyl, and inparticular methyl, ethyl, methoxy, ethoxy, chlorine, bromine, hydroxylor carboxyl.

Fibre-reactive radicals are also substituents of the radicals D₁ and D₂.

Fibre-reactive radicals are to be understood as meaning those which arecapable of reacting with the hydroxyl groups of cellulose, the amino,carboxyl, hydroxyl and thiol groups in wool and silk, or with the aminoand possibly carboxyl groups of synthetic polyamides to form covalentchemical bonds. The fibre-reactive radicals are as a rule bonded to thedye radical directly or by a bridged member. Suitable fibre-reactiveradicals are, for example, those which contain at least one substituentwhich can be split off on an aliphatic, aromatic or heterocyclicradical, or in which the radicals mentioned contain a radical which issuitable for reaction with the fibre material, for example a vinylradical.

Preferred fibre-reactive radicals for D₁ and D₂ are the radicals of theformula (4a), (4b), (4c), (4d), (4e), (4f) or (4g)

—SO₂—Y  (4a),

—NH—CO—(CH₂)_(l)—SO₂—Y  (4b),

—CONR₈—(CH₂)_(m)—SO₂—Y  (4c),

—NH—CO—CH(Hal)—CH₂-Hal  (4d),

—NH—CO—C(Hal)═CH₂  (4e),

in which

Hal is chlorine or bromine;

X₂ is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl;

T₁ independently is as defined for X₂ or is a substituent which is notfibre-reactive or a fibre-reactive radical of the formula (5a), (5b),(5c), (5d), (5e) or (5f)

 in which

R₈ and R₁₀ independently of one another are each hydrogen, C₁-C₄alkylwhich is unsubstituted or substituted by hydroxyl, sulfo, sulfato,carboxyl or cyano or a radical

 R₉ and R₁₂ independently of one another are each hydrogen orC₁-C₄alkyl,

R₁₁, is hydrogen, hydroxyl, sulfo, sulfato, carboxyl, cyano, halogen,C₁-C₄alkoxycarbonyl, C₁-C₄alkanoyloxy, carbamoyl or the group —SO₂—Y,

alk and alk₁ independently of one another are linear or branchedC₁-C₆alkylene,

arylen is a phenylene or naphthylene radical which are unsubstituted orsubstituted by sulfo, carboxyl, C₁-C₄alkyl, C₁-C₄alkoxy or halogen,

Q is a radical —O— or —NR₁₂—, in which R₁₂ is as defined above,

W is a group —SO₂—NR₈—, —CONR₈— or —NR₈CO—, in which R₈ is as definedabove,

Y is vinyl or a radical —CH₂—CH₂—U and U is a group which can be splitoff under alkaline conditions,

Y₁ is a group —CH(Hal)- CH₂- Hal or —C(Hal)═CH₂ and Hal is chlorine orbromine and

l and m independently of one another are an integer from 1 to 6 and n isthe number 0 or 1; and

X₃ is halogen or C₁-C₄alkylsulfonyl;

X₄ is halogen or C₁-C₄alkyl and

T₂ is hydrogen, cyano or halogen.

A group U which can be split off under alkaline conditions is, forexample, —Cl, —Br, —F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅,—OSO₂—C₁—C₄alkyl or —C₄alkyl)₂. U is preferably a group of the formula—Cl, —OSO₃H, —SSO₃H, —OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂, in particular —Clor —OSO₃H, and particularly preferably —OSO₃H.

Examples of suitable radicals Y are accordingly vinyl, β-bromo- orβ-chloroethyl, β-acetoxyethyl, β-benzoyloxyethyl, β-phosphatoethyl,β-sulfatoethyl and β-thiosulfatoethyl. Y is preferably vinyl,β-chloroethyl or β-sulfatoethyl, and in particular vinyl orβ-sulfatoethyl.

R₈ and R₁₀ independently of one another are preferably hydrogen orC₁-C₄alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl or tert-butyl and particularly preferably hydrogen, methyl orethyl. R₈ and R₁₀ are particularly preferably hydrogen.

R₉ and R₁₂ independently of one another are each preferably hydrogen,methyl or ethyl, and particularly preferably hydrogen.

R₁₁ is preferably hydrogen.

l and m independently of one another are preferably the number 2, 3 or4, and particularly preferably the number 2 or 3.

Especially preferably, l is the number 3 and m is the number 2.

A non-reactive substituent T₁ can be, for example, hydroxyl;C₁-C₄alkoxy; C₁-C₄alkylthio which is unsubstituted or substituted byhydroxyl, carboxyl or sulfo; amino; amino which is mono- ordisubstituted by C₁-C₈alkyl, in which the alkyl is unsubstituted orfurther substituted, for example, by sulfo, sulfato, hydroxyl, carboxylor phenyl, in particular by sulfo or hydroxyl, and may be interrupted bya radical —O—; cyclohexylamino; morpholino; N—C₁-C₄alkyl-N-phenylaminoor phenylamino or naphthylamino, in which the phenyl or naphthyl areunsubstituted or substituted, for example by C₁-C₄-alkyl, C₁-C₄-alkoxy,carboxyl, sulfo or halogen.

Examples of suitable non-reactive substituents T₁ are amino,methylamino, ethylamino, β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, β-sulfoethylamino, cyclohexylamino,morpholino, 2-, 3- or 4-chlorophenylamino, 2-, 3- or4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or4-sulfophenylamino, disulfophenylamino, 2-, 3- or 4-carboxyphenylamino,1- or 2-naphthylamino, 1-sulfo-2-naphthylamino,4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino,N-methyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxyl.

A radical T₁ which is not fibre-reactive is preferably C₁-C₄alkoxy,C₁-C₄-alkylthio which is unsubstituted or substituted by hydroxyl,carboxyl or sulfo, hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylaminowhich are unsubstituted or substituted in the alkyl moiety by hydroxyl,sulfato or sulfo, morpholino, phenylamino or N—C₁-C₄alkyl-N-phenylamino,which are unsubstituted or substituted in the phenyl ring by sulfo,carboxyl, acetylamino, chlorine, methyl or methoxy and in which thealkyl is unsubstituted or substituted by hydroxyl, sulfo or sulfato, ornaphthylamino which is unsubstituted or substituted by 1 to 3 sulfogroups.

Particularly preferred radicals T₁ which are not fibre-reactive areamino, N-methylamino, N-ethylamino, N-β-hydroxyethylamino,N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, morpholino, 2-, 3- or 4-carboxyphenylamino,2-, 3- or 4-sulfophenylamino or N—C₁-C₄-alkyl-N-phenylamino.

Halogen X₂ is, for example, fluorine, chlorine or bromine, and inparticular chlorine or fluorine.

X₂ is preferably chlorine or fluorine.

Halogen T₂, X₃ and X₄ are, for example, fluorine, chlorine or bromine,in particular chlorine or fluorine.

C₁-C₄alkylsulfonyl X₃ is, for example, ethylsulfonyl or methylsulfonyl,and in particular methylsulfonyl.

C₁-C₄alkyl X₄ is, for example, methyl, ethyl, n- or iso-propyl or n-,iso- or tert-butyl, and in particular methyl.

X₃ and X₄ are preferably independently of one another chlorine orfluorine.

T₂ is preferably cyano or chlorine.

Hal is preferably bromine.

Alk and alk₁ independently of one another are, for example, a methylene,ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexyleneradical or branched isomers thereof.

Alk and alk₁ independently of one another are preferably each aC₁-C₄alkylene radical, and particularly preferably an ethylene orpropylene radical.

Arylen is preferably a 1,3- or 1,4-phenylene radical which isunsubstituted or substituted, for example by sulfo, methyl, methoxy orcarboxyl, and particularly preferably an unsubstituted 1,3- or1,4-phenylene radical.

Q is preferably —NH— or —O—, and particularly preferably —O—.

W is preferably a group of the formula —CONH— or —NHCO—, in particular agroup of the formula —CONH—.

n is preferably the number 0.

The reactive radicals of the formulae (5a) to (5f) are preferably thosein which W is a group of the formula —CONH—, R₁₀, R₁₁ and R₁₂ are eachhydrogen, Q is the radical —O— or —NH—, alk and alk₁ independently ofone another are each ethylene or propylene, arylen is phenylene which isunsubstituted or substituted by methyl, methoxy, carboxyl or sulfo, Y isvinyl or β-sulfatoethyl, Y₁ is —CHBr—CH₂Br or —CBr═CH₂ and n is thenumber 0.

Fibre-reactive radicals for D₁ and D₂ are particularly preferablyradicals of the formula (4a), (4b), (4c), (4d), (4e) or (4f), in which Yis vinyl, β-chloroethyl or β-sulfatoethyl, Hal is bromine, R₈ and R₉ arehydrogen, l and m are the number 2 or 3, X₂ is halogen, T₁ isC₁-C₄alkoxy, C₁-C₄alkylthio which is unsubstituted or substituted byhydroxyl, carboxyl or sulfo, hydroxyl, amino, N-mono- or N,N- di-C₁-C₄-alkylamino which are unsubstituted or substituted in the alkylmoiety by hydroxyl, sulfato or sulfo, morpholino, phenylamino orN—C₁-C₄alkyl-N-phenylamino which are unsubstituted or substituted in thephenyl ring by sulfo, carboxyl, chlorine, acetylamino, methyl or methoxyand in which the alkyl is unsubstituted or substituted by hydroxyl,sulfo or sulfato, naphthylamino which is unsubstituted or substituted by1 to 3 sulfo groups, or a fibre-reactive radical of the formula (5a′),(5b′), (5c′), (5d′) or (5f′)

—NH—(CH₂)₂₋₃—SO₂Y  (5a′),

—NH—(CH₂)₂₋₃—O—(CH₂)₂₋₃—SO₂Y  (5b′),

in particular a fibre-reactive radical of the formula (5c′) or (5d′), inwhich

Y is vinyl, β-chloroethyl or β-sulfatoethyl and

Y₁ is a group —CH(Br)—CH₂—Br or —C(Br)═CH₂.

In the case of the radicals of the formula (5a′) and (5b′), Y ispreferably β-chloroethyl. In the case of the radicals of the formulae(5c′) and (5d′), Y is preferably vinyl or β-sulfatoethyl.

D₁ and D₂ preferably contain at least one fibre-reactive radical.

D₁ and D₂ are preferably a phenyl or naphthyl radical which areunsubstituted or further substituted by substituents customary in dyes,for example C₁-C₄alkyl, C₁-C₄alkoxy, halogen, sulfo, nitro, carboxyl ora fibre-reactive radical of the formula (4a), (4b), (4c), (4d), (4e),(4f) or (4g), where the fibre-reactive radicals mentioned are as definedand preferred above.

A radical D₁ or D₂ of a substituted or unsubstituted diazo component ofthe benzene or naphthaline series also includes monoazo radicals, forexample those of the formula (6) or (7)

—D*—N═N—K*  (6)

or

D*—N═N—K**—  (7),

preferably of the formula (7), in which D* is the radical of a diazocomponent of the benzene or naphthaline series, K* is the radical of acoupling component of the benzene, naphthaline, pyrazolone,6-hydroxypyrid-2-one or acetoacetic acid arylamide series and K** is theradical of the coupling component of the benzene or naphthaline series,where D*, K* and K** can carry substituents customary in dyes.

Substituents for D*, K* and K** which are not fibre-reactive arepreferably C₁-C₄alkyl or C₁-C₄alkoxy which are unsubstituted or furthersubstituted by hydroxyl, C₁-C₄alkoxy, sulfo or sulfato, halogen,carboxyl, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl,amino, ureido, hydroxyl, sulfomethyl, C₂-C₄alkanoylamino,C₁-C₄alkylsulfonylamino, benzoylamino which is unsubstituted orsubstituted in the phenyl ring by C₁-C₄alkyl, C₁-C₄alkoxy, halogen orsulfo or phenyl which is unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxyl or sulfo.

Fibre-reactive substituents for D*, K* and K** a re preferably theradicals of the formula (4a), (4c), (4d), (4e) or (4f), in particular(4a), where the radicals mentioned are as defined and preferred above.

The monoazo radicals of the formula (6) or (7) preferably contain atleast one sulfo group.

Preferred monoazo radicals D₁ and D₂ of the formula (7) are the radicalsof the formula (7a), (7b), (7c), (7d), (7e), (7f), (7g), (7h), (7i) or(7j)

in which (R₁₃)₀₋₂ is 0 to 2 identical or different substituents from thegroup consisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyl and sulfoand Z₁, is a fibre-reactive radical of the formula (4a), (4c), (4d),(4e) or (4f), where the fibre-reactive radicals mentioned are as definedand preferred above,

in which (R₁₃)₀₋₂ is as defined above, (R₁₄)₀₋₃ is 0 to 3 identical ordifferent substituents from the group consisting of halogen, nitro,cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁-C₄alkyl, C₁-C₄alkoxywhich is unsubstituted or substituted by hydroxyl, sulfato orC₁-C₄alkoxy, amino, C₂-C₄alkanoylamino, ureido, hydroxyl, carboxyl,sulfomethyl, C₁-C₄alkylsulfonylamino, sulfo and a fibre-reactive radicalof the formula (4f′)

in which

X′₂ is fluorine or chlorine and

T′₁ is amino, N-mono- or N,N- di- C₁-C₄alkylamino which is unsubstitutedor substituted in the alkyl moiety by hydroxyl, sulfato or sulfo,morpholino, phenylamino or N—C₁-C₄alkyl-N-phenylamino which areunsubstituted or substituted in the phenyl ring by sulfo, carboxyl,acetylamino, chlorine, methyl or methoxy and in which the alkyl isunsubstituted or substituted by hydroxyl, sulfo or sulfato ornaphthylamino which is unsubstituted or substituted by 1 to 3 sulfogroups and

Z₁ is as defined above.

The numbers on the naphthyl rings of the radicals of the formulae (7a),(7b), (7e) and (7f) identify the possible bonding positions.

The radicals D₁ and D₂ independently of one another are preferably eacha radical of the formula (8) or (9)

in particular of the formula (9), in which

(R₁₃)₀₋₂ and (R₁₅)₀₋₂ independently of one another are 0 to 2 identicalor different substituents chosen from the group consisting of halogen,C₁-C₄alkyl, C₁-C₄alkoxy, carboxyl and sulfo;

K is the radical of a coupling component of the formula (10a) or (10b)

in which

R₁₄ is hydrogen, sulfo or C₁-C₄alkoxy which is unsubstituted orsubstituted in the alkyl moiety by hydroxyl or sulfato and

R′₁₄ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, ureido ora radical of the formula (4f′), in which X′₂ and T′₁ are as definedabove; and

Z and Z₁ independently of one another are a radical of the formula (4a),(4b), (4c), (4d), (4e) or (4f), in which

R₈ and R₉ are hydrogen,

Hal is bromine,

Y is vinyl, β-chloroethyl or β-sulfatoethyl,

l and m independently of one another are the number 2 or 3,

X₂ is chlorine or fluorine and

T₁ is C₁-C₄alkoxy, C₁-C₄alkylthio which is unsubstituted or substitutedby hydroxyl, carboxyl or sulfo, hydroxyl, amino, N-mono- or N,N- di-C₁-C₄alkylamino, which are unsubstituted or substituted in the alkylmoiety by hydroxyl, sulfato or sulfo, morpholino, phenylamino orN—C₁-C₄alkyl-N-phenylamino which are unsubstituted or substituted in thephenyl ring by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxyand in which the alkyl is unsubstituted or substituted by hydroxyl,sulfo or sulfato, naphthylamino which is unsubstituted or substituted by1 to 3 sulfo groups, or a fibre-reactive radical of the formula (5c′) or(5d′)

in which

Y is as defined above, and in particular is vinyl or β-sulfatoethyl.

C₁-C₄alkyl R₁₃, R′₁₄ and R₁₅ independently of one another are, forexample, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl or isobutyl, preferably methyl or ethyl, and in particularmethyl.

C₁-C₄alkoxy R₁₃, R₁₄, R′₁₄ and R₁₅ independently of one another are, forexample, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or isobutoxy,preferably methoxy or ethoxy, and in particular methoxy. R₁₄ isunsubstituted or may be substituted in the alkyl moiety by hydroxyl orsulfato.

Halogen R₁₃ and R₁₅, independently of one another are, for example,fluorine, chlorine or bromine, preferably chlorine or bromine, and inparticular chlorine.

C₂-C₄alkanoylamino R′₁₄ is, for example, acetylamino or propionylamino,in particular acetylamino.

In the radical of the coupling component of the formula (10b), the sulfogroup in ring ii is preferably bonded in the 3 or 4-position. If thering ii contains a sulfo group, the radical of the formula (10b) ispreferably bonded to ring ii in the 1, 2 or 3-position. If no sulfo ispresent in the ring ii, the radical of the formula (10b) is preferablybonded in the 1-, 2 or 3-position on ring ii.

The radicals D₁ and D₂ independently of one another are particularlypreferably each a radical of the formula (9a), (9b), (9c), (9d), (9e) or(9f)

in which (R₁₅)₀₋₂ and (R₁₆)₀₋₂ independently of one another are 0 to 2identical or different substituents chosen from the group consisting ofhalogen, C₁-C₄alkyl, C₁-C₄alkoxy and sulfo, in particular methyl,methoxy and sulfo,

Y is vinyl, β-chloroethyl or β-sulfatoethyl,

Y₁ is a group —CH(Br)—CH₂—Br or —C(Br)═CH₂,

l is the number 2 or 3, in particular 3, and

m is the number 2 or 3, in particular 2.

The numbers in the radicals of the formulae (9a), (9c), (9d), (9e) and(9f) identify the possible bonding positions of the fibre-reactiveradical.

In the case of the radicals of the formulae (9a), (9b), (9d) and (9f), Yis preferably vinyl or β-sulfatoethyl.

In the case of the radical of the formula (9c), Y is preferablyβ-chloroethyl.

D₁ and D₂ independently of one another are preferably in each case aradical of the formula (9a) or (9b), and in particular (9a).

R₂ is preferably hydrogen or C₁-C₄alkyl, particularly preferablyhydrogen, methyl or ethyl, and especially preferably hydrogen.

R₃ is preferably cyano or carbamoyl, and in particular cyano.

C₁-C₄alkyl R₄ and R₇ independently of one another are, for example,methyl, ethyl, n- or iso-propyl or n-, sec-, tert- or iso-butyl,preferably methyl or ethyl, and in particular methyl.

R₄ is preferably methyl, ethyl or amino, and in particular methyl.

N-Mono- or N,N—di—C₁-C₄alkylamino R₅ is unsubstituted or substituted inthe alkyl moiety, for example by C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, hydroxyl, sulfo, sulfato or carboxyl, preferablyhydroxyl, sulfo or sulfato, and in particular hydroxyl. Examples are thefollowing radicals: N-methylamino, N,N-dimethylamino, N-ethylamino,N-β-hydroxyethylamino, N,N-di-β-hydroxyethylamino,N-β-sulfatoethylamino, N-β-sulfoethylamino or N-β-carboxyethylamino.

R₅ is preferably amino or N-mono-C₁-C₄alkylamino which is unsubstitutedor substituted in the alkyl moiety by hydroxyl, sulfo or sulfato, and inparticular amino or N-β-hydroxyethylamino.

R₆ is preferably carbamoyl or sulfomethyl, in particular carbamoyl.

R₇ is preferably methyl or ethyl, and in particular methyl.

The formazan radical in the dye of the formula (1) is preferably aradical of the formula (11) or (12)

preferably a radical of the formula (12).

The formazan radicals in the dyes of the formula (1) according to theinvention are particularly preferably the radicals of the formula (12a)or (12b)

in particular (12a).

The dyes of the formula (1) according to the invention preferably havethe formula (1a)

in which

X₁ is fluorine or chlorine,

R₁ is hydrogen or R₁ is as defined for A and

A is a radical of the formula (2a′), (2b′) or (3a)

 in which

B₁ and B₂ are straight-chain or branched C₂-C₆alkylene,

D₁ and D₂ independently of one another are each a radical of the formula(9a), (9b), (9c), (9d), (9e) or (9f), where the radicals mentioned areas defined and preferred above,

R₅ is amino or N-β-hydroxyethylamino and

R₆ is carbamoyl or sulfomethyl, in particular carbamoyl.

The dyes of the formula (1), according to the invention particularlypreferably have the formula (1a′)

in which

X₁, R₁, and A are as defined and preferred above under formula (1a).

The present invention furthermore relates to a process for thepreparation of the dyes according to the invention, which comprisesreacting in each case about 1 molar equivalent of a compound of theformula (13)

a compound of the formula (14)

and an amine of the formula (15)

with one another in any sequence, where A, Me, R₁, u and q are asdefined and preferred above and X is halogen, in particular fluorine orchlorine.

The individual process steps defined above can be carried out in varioussequences, and where appropriate in some cases also simultaneously, sothat various process variants are possible. In general, the reaction iscarried out stepwise in succession, the sequence of the simple reactionsbetween the individual reaction components advantageously depending onthe particular conditions.

One process variant comprises subjecting a compound of the formula (13)to a condensation reaction with cyanuric chloride or cyanuric fluorideand reacting the resulting product with a compound of the formula (15).

The condensation reactions between the compounds of the formulae (13),(14) and (15) in general are carried out analogously to known processes,as a rule in aqueous solution at temperatures of, for example, 0 to 30°C. and a pH of, for example, 3 to 7. Instead of the compound of theformula (15), it is also possible to employ the correspondingintermediate of the formula (17a), (17b) or (18)

in the process and to produce the radical A only in the subsequentcourse of the process, by diazotization of an amine of the formula (16a)or (16b)

D₁—NH₂  (16a)

or

D₂—NH₂  (16b)

and subsequent coupling reactions. The radicals B₁, B₂, D₁, D₂, R₂, R₃,R₄, R₅, R₆ and R₇ are as defined above.

The compound of the formula (15) in which A is a radical of the formula(2a), (2b) or (3) is obtained by diazotizing an amine of the formula(16a) and coupling the diazotization product to a compound of theformula (17a) or (17b), or by diazotizing an amine of the formula (16b)and coupling the diazotization product to a compound of the formula(18).

The diazotization of the compound of the formula (16a) or (16b) and itscoupling to the compound of the formula (17a), (17b) or (18), or to thecondensation product obtained according to the procedure described abovefrom the compound of the formula (17a), (17b) or (18) are carried out inthe customary manner, for example by diazotizing the compound of theformula (16a) or (16b) in mineral acid solution, for examplehydrochloric acid solution, with a nitrite, for example sodium nitrite,at a low temperature, for example at 0 to 5° C., and then coupling thediazotization product with the corresponding coupling component at aneutral to slightly acid pH, for example at pH 3 to 7, and lowtemperatures, for example 0 to 30° C.

The compounds of the formulae (13), (16a), (16b), (17a), (17b) and (18)are known or can be prepared analogously to known compounds.

The compounds of the formulae (17a) and (17b) as a rule are obtained asa mixture in the preparation.

The triazinyl compounds obtainable by the process described above stillcontain a halogen atom which can be converted into a group X₁ byreaction with a compound of the formulae X₁-H at elevated temperature,preferably 20 to 70° C., and a neutral to slightly alkaline pH, whichis, for example, 7 to 9, depending on the compound of the formula X₁-Hemployed, where X₁ is as defined above, except for halogen. An excess ofthe compound of the formula X₁-H is advantageously employed.

If appropriate, the end product can also be subjected to a conversionreaction. Such a conversion reaction is, for example, the conversion ofa vinylatable reactive group contained in D₁ or D₂ into its vinyl formby treatment with dilute sodium hydroxide solution, for exampleconversion of the β-sulfatoethylsulfonyl- or β-chloroethylsulfonyl groupinto the vinylsulfonyl radical. Such reactions are known per se.

The compounds of the formula (1) according to the invention are suitableas dyes for dyeing and printing widely varying materials, such as fibrematerials containing hydroxyl groups or containing nitrogen. Examples offibre materials containing nitrogen are silk, leather, wool, polyamidefibres and polyurethanes. The dyes according to the invention areparticularly suitable for dyeing and printing all types of cellulosicfibre materials. Such cellulosic fibre materials are, for example, thenatural cellulose fibres, such as cotton, linen and hemp, and pulp andregenerated cellulose, preferably cotton. The dyes according to theinvention are also suitable for dyeing or printing cellulosic blendfabrics, for example mixtures of cotton and polyamide fibres, or inparticular cotton/polyester blends.

The dyes according to the invention can be applied to the fibre materialand fixed on the fibre in various ways, in particular in the form ofaqueous dye solutions and printing pastes. They are suitable both forthe exhaust method and for dyeing by the padder dyeing method, in whichthe goods are impregnated with aqueous dye solutions, which may containsalts, and the dyes are fixed, after an alkali treatment or in thepresence of alkali, if appropriate with the action of heat or by storageat room temperature for several hours. After the fixing, the dyeings orprints are rinsed thoroughly with cold and hot water, if appropriatewith the addition of an agent which has a dispersing action and promotesdiffusion of the non-fixed portions.

The dyes according to the invention are distinguished by a highreactivity, good fixing capacity and very good build-up capacity. Theycan therefore be employed by the exhaust dyeing method at low dyeingtemperatures and require only short steaming times in the pad-steamprocess. The degrees of fixing are high and the non-fixed portions caneasily be washed out, the difference between the degree of exhaustionand degree of fixing being remarkably small, i.e. the soaping loss beingvery low. The dyes according to the invention are also particularlysuitable for printing, in particular on cotton, and also for printingfibres containing nitrogen, for example wool or silk or blend fabricswhich comprise wool or silk.

The dyeings and prints produced with the dyes according to the inventionhave a high colour strength and a high fibre-dye bond stability both inthe acid and in the alkaline range, and furthermore a good fastness tolight and very good wetfastness properties, such as fastness to washing,water, seawater, cross-dyeing and perspiration, and a good fastness topleating, fastness to ironing and fastness to rubbing.

The following examples serve to illustrate the invention. Thetemperatures are stated in degrees Celsius, parts are parts by weightand the percentage data relate to the percentages by weight, unlessstated otherwise. Parts by weight may be the same ratio to parts byvolume as the kilogram to the litre.

EXAMPLE 1

36.3 parts of an amine of the formula D₁₀—NH₂, in which D₁₀ is a radicalof the formula

are dissolved under neutral conditions in 350 parts of water, with theaddition of a sodium carbonate solution, and 7 parts of sodium nitriteare added. This solution is added dropwise to a mixture of 300 parts ofice/water and 30 parts of concentrated hydrochloric acid. The reactionmixture is stirred at 0° C. for one hour.

EXAMPLE 2

25 parts of a N sodium nitrite solution are added to a neutral solutionof 41.2 parts of an amine of the formula D₁₁—NH₂, in which D₁₁ is aradical of the formula

in 400 parts of water. This solution is added dropwise to a mixture of300 parts of ice/water and 30 parts of concentrated hydrochloric acid.The reaction mixture is stirred at 0° C. for one hour.

EXAMPLES 3 TO 27

Diazo compounds of the amines defined in Table 1 can be preparedanalogously to the procedure described in Examples 1 or 2 when anequimolar amount of the amines of the formula D_(xy)—NH₂ defined inTable 1 is used in place of the amines of the formula D₁₀—NH₂ or D₁₁—NH₂defined in Examples 1 or 2.

TABLE 1 Amine Example D_(xy)-NH₂ D_(xy)  3 D₁₂-NH₂

 4 D₁₃-NH₂

 5 D₁₄-NH₂

 6 D₁₅-NH₂

 7 D₁₆-NH₂

 8 D₁₇-NH₂

 9 D₁₈-NH₂

10 D₁₉-NH₂

11 D₂₀-NH₂

12 D₂₁-NH₂

13 D₂₂-NH₂

14 D₂₃-NH₂

15 D₂₄-NH₂

16 D₂₅-NH₂

17 D₂₆-NH₂

18 D₂₇-NH₂

19 D₂₈-NH₂

20 D₂₉-NH₂

21 D₃₀-NH₂

22 D_(31a)-NH₂-D_(31r)-NH₂

T₁:  22a D_(31a)-NH₂

 22b D_(31b)-NH₂

 22c D_(31c)-NH₂

 22d D_(31d)-NH₂

 22e D_(31e)-NH₂ D_(31e) —NHCH₂CH₂OH 22f D_(31f)-NH₂ D_(31f)—N(CH₂CH₂OH)₂  22g D_(31g)-NH₂

 22h D_(31h)-NH₂

 22i D_(31i)-NH₂ D_(31i) —NH—(CH₂)₂—O—(CH₂)₂—OH  22j D_(31j)-NH₂ D_(31j)—NHCH₂CH₂SO₃H  22k D_(31k)-NH₂

 22l D_(31l)-NH₂

  22m D_(31m)-NH₂ D_(31m) —NH—(CH₂)₂—SO₂—(CH₂)₂—Cl  22n D_(31n)-NH₂D_(31n) —NH—(CH₂)₂—O—(CH₂)₂—SO₂—(CH₂)₂—Cl  22o D_(31o)-NH₂

 22p D_(31p)-NH₂

 22q D_(31q)-NH₂

22r D_(31r)-NH₂

23 D₃₂-NH₂

24 D₃₃-NH₂

25 D₃₄-NH₂

26 D₃₅-NH₂

27 D₃₆-NH₂

EXAMPLE 28a

The acid diazo compound suspension obtained according to Example 1 isadded dropwise to a solution of 21.3 parts of pyridone couplingcomponent of the formula

in 600 parts of water. The temperature is kept at 5° C. and the pH iskept at 3 to 5 by addition of a sodium hydroxide solution. Thesuspension of a yellow dye which, in the form of the free acid, has theformula

is obtained.

EXAMPLE 28b

Analogously to the procedure described in Example 28a, from the pyridonecoupling compound of the formula

the suspension of a yellow dye which, in the form of the free acid, hasthe formula

is obtained.

EXAMPLE 29

The acid diazo compound suspension obtained according to Example 2 isadded dropwise to a cold solution of 21 parts of the pyridone couplingcomponent from Example 28a in 300 parts of water, the pH being kept at 7by addition of a sodium hydroxide solution. The reaction mixture isstirred for one hour, during which it is allowed to warm to 20° C. Thesuspension of a yellow dye which, in the form of the free acid, has theformula

is obtained.

EXAMPLE 30

56.4 parts of 3-cyano-2,6-dichloro-4-methylpyridine are added inportions to 130 parts of ethanolamine at 25° C. in the course of onehour and the mixture is stirred for one hour. The reaction mixture isdischarged onto 900 parts of water and stirred. The product which hasprecipitated out is filtered off and dried in vacuo. 60 parts of amixture of the compounds of the formulae

are obtained and are introduced into 250 parts of 1,3-propylenediamineat 100° C. After one hour, the excess 1,3-propylenediamine is distilledoff under reduced pressure. 55 parts of a mixture of the compounds ofthe formulae

are obtained from the resulting oil by reprecipitation in isopropanolwith hydrochloric acid.

EXAMPLE 31

14 parts of trifluorotriazine are added dropwise to a neutral solutionof 60 parts of the copper complex of5-amino-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonicacid and 5 parts of disodium hydrogen phosphate in 500 parts of water ata temperature below 2° C., the pH being kept constant by addition of asodium hydroxide solution. The solution of a compound which, in the formof the free acid, has the formula

is obtained.

EXAMPLE 32

19 parts of cyanuric chloride are stirred vigorously into 50 parts ofwater at a temperature of 0° C., with the addition of a wetting agentand 5 parts of disodium hydrogen phosphate. A neutral solution of 60parts of the copper complex of5-amino-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonicacid in 500 parts of water is added dropwise. The temperature is kept at2 to 5° C. and the pH is kept at 5 by addition of sodium hydroxidesolution. The solution of a compound which, in the form of the freeacid, has the formula

is obtained.

EXAMPLE 33a

The solution obtained according to Example 31 is added to the yellow dyesuspension obtained according to Example 28a, the pH being kept at 7 to8 by addition of a sodium hydroxide solution. The temperature is 20 to30° C. The resulting solution is then freed from the salt by dialysisand freeze dried. 110 parts of a compound which, in the form of the freeacid, has the formula (101)

and dyes cotton in green colour shades with good all-round propertiesare obtained.

EXAMPLE 33b

A dye which, in the form of the free acid, has the formula (102)

and dyes cotton in green colour shades with good all-round properties isobtained analogously to the procedure described in Example 33a from thesuspension obtained according to Example 28b.

EXAMPLE 34

The solution obtained according to Example 32 is added to the yellow dyesuspension obtained according to Example 29, the pH being kept at 7.5 to8 by addition of a sodium hydroxide solution and the temperature beingkept at 30 to 40° C. 240 parts of sodium chloride are added to theresulting dye solution. After one hour, the dye which has precipitatedout is filtered off and dried in vacuo at 60° C. 160.8 parts of acompound which, in the form of the free acid, has the formula (103)

and dyes cotton in green colour shades with good all-round propertiesare obtained.

EXAMPLE 35

The acid diazo compound suspension obtained according to Example 1 iscoupled to 29.4 parts of the mixture of pyridine compounds from Example30 analogously to the procedure described in Example 28a, and theresulting suspension of the azo dyes is further reacted directly,analogously to the procedure described in Example 33, with a solution ofthe formazan compound obtained according to Example 31. 167 parts of adye powder which essentially comprises compounds which, in the form ofthe free acid, have the formulae (104) and (105)

and dyes cotton in green colour shades with good all-round propertiesare obtained.

EXAMPLES 36 to 123

The dyes of the following general formula (106)

which D_(xy) and X in each case are the radicals listed in Table 2 andthe radical D_(xy) in each case is as defined in Examples 1 to 27 areobtained from the diazo compounds described in Examples 1 to 27analogously to the procedure described in Examples 28a, 29, 33a and 34.The dyes dye cotton and wool in green colour shades with good all-roundproperties.

TABLE 2 Example D_(xy) X 36 D₁₀ Cl 37 D₁₁ F 38 D₁₂ F 39 D₁₃ F 40 D₁₄ F41 D₁₅ F 42 D₁₆ F 43 D₁₇ F 44 D₁₈ F 45 D₁₉ F 46 D₂₀ F 47 D₂₁ F 48 D₂₂ F49 D₂₃ F 50 D₂₄ F 51 D₂₅ F 52 D₂₆ F 53 D₂₇ F 54 D₂₈ F 55 D₂₉ F 56 D₃₀ F57 D_(31a) F 58 D_(31b) F 59 D_(31c) F 60 D_(31d) F 61 D_(31e) F 62D_(31f) F 63 D_(31g) F 64 D_(31h) F 65 D_(31i) F 67 D_(31j) F 68 D_(31k)F 69 D_(31l) F 70 D_(31m) F 71 D_(31n) F 72 D_(31o) F 73 D_(31p) F 74D_(31q) F 75 D_(31r) F 76 D₃₂ F 77 D₃₃ F 78 D₃₄ F 79 D₃₅ F 80 D₃₆ F 81D₁₂ Cl 82 D₁₃ Cl 83 D₁₄ Cl 84 D₁₅ Cl 85 D₁₆ Cl 86 D₁₇ Cl 87 D₁₈ Cl 88D₁₉ Cl 89 D₂₀ Cl 90 D₂₁ Cl 91 D₂₂ Cl 92 D₂₃ Cl 93 D₂₄ Cl 94 D₂₅ Cl 95D₂₆ Cl 96 D₂₇ Cl 97 D₂₈ Cl 98 D₂₉ Cl 99 D₃₀ Cl 100  D_(31a) Cl 101 D_(31b) Cl 102  D_(31c) Cl 103  D_(31d) Cl 104  D_(31e) Cl 105  D_(31f)Cl 106  D_(31g) Cl 107  D_(31h) Cl 108  D_(31i) Cl 109  D_(31j) Cl 110 D_(31k) Cl 111  D_(31l) Cl 112  D_(31m) Cl 113  D_(31n) Cl 114  D_(31o)Cl 116  D_(31p) Cl 117  D_(31q) Cl 118  D_(31r) Cl 119  D₃₂ Cl 120  D₃₃Cl 121  D₃₄ Cl 122  D₃₅ Cl 123  D₃₆ Cl

EXAMPLES 124 TO 155

A dye composition which essentially comprises compounds which, in theform of the free acid, have the formulae (107) and (108)

in which D_(xy) in each case is the radicals listed in Table 3 and theseradicals are in each case as defined in Examples 2 to 27, are obtainedfrom the diazo compounds described in Examples 2 to 27 analogously tothe procedure described in Example 35. The dyes dye cotton in greencolour shades with good all-round properties.

TABLE 3 Example D_(xy) 124 D₁₁ 125 D₁₂ 126 D₁₄ 127 D₁₆ 128 D₁₈ 129 D₂₃130 D₂₅ 131 D₂₈ 132 D₂₉ 133 D₃₀ 134 D_(31a) 135 D_(31b) 136 D_(31c) 137D_(31d) 138 D_(31e) 139 D_(31f) 140 D_(31g) 141 D_(31h) 142 D_(31i) 143D_(31j) 144 D_(31k) 145 D_(31l) 146 D_(31m) 147 D_(31n) 148 D_(31o) 149D_(31p) 150 D_(31q) 151 D_(31r) 152 D₃₂ 153 D₃₃ 154 D₃₄ 155 D₃₅

EXAMPLES 156 TO 171

Dyes which, in the form of the free acid, have the general formula (109)

in which D_(xy), F_(x) and X are each the radicals defined in Table 4,where D_(xy) in each case is as defined in Examples 1 and 2 and theradical F_(x) in each case is one of the formazan radicals definedbelow, are obtained from the copper-formazan complexes of the formulaF_(x)—NH₂ analogously to the procedure described in Examples 31, 32, 33aand 34. The dyes dye cotton in green colour shades with good all-roundproperties.

TABLE 4 Example D_(xy) F_(x) X 156 D₁₀ F₁ F 157 D₁₀ F₂ F 158 D₁₀ F₃ F159 D₁₀ F₄ F 160 D₁₀ F₁ Cl 161 D₁₀ F₂ Cl 162 D₁₀ F₃ Cl 163 D₁₀ F₄ Cl 164D₁₁ F₁ F 165 D₁₁ F₂ F 166 D₁₁ F₃ F 167 D₁₁ F₄ F 168 D₁₁ F₁ Cl 169 D₁₁ F₂Cl 170 D₁₁ F₃ Cl 171 D₁₁ F₄ Cl

Dyeing Instructions 1

100 parts of cotton fabric are introduced at 60° C. into 1500 parts of adye bath which comprises 45 g/l of sodium chloride and 2 parts of thereactive dye obtained according to Example 33a. After 45 minutes at 60°C., 20 g/l of calcined sodium carbonate are added. Dyeing is continuedat this temperature for 45 minutes. Thereafter, the dyed goods arerinsed, soaped at the boil with a nonionic detergent for a quarter of anhour, rinsed again and dried.

As an alternative to the instructions described, dyeing can also becarried out at 80° C. instead of at 60° C.

Dye Instructions II

0.1 part of the dye according to Example 33a is dissolved in 200 partsof water, and 0.5 part of sodium sulfate, 0.1 part of a levellingauxiliary (based on the condensation product of a higher aliphatic amineand ethylene oxide) and 0.5 part of sodium acetate are added. The pH isthen brought to a value of 5.5 with acetic acid (80%). The dyebath isheated at 50° C. for 10 minutes and 10 parts of a woolen fabric are thenadded. The dyebath is heated to a temperature of 100° C. in the courseof about 50 minutes and dyeing is carried out at this temperature for 60minutes. Thereafter, the dyebath is allowed to cool to 90° C. and thedyed goods are removed. The woollen fabric is washed with warm and coldwater and then spun and dried.

Printing Instructions

3 parts of the dye obtained according to Example 33a are sprinkled withrapid stirring into 100 parts of a stock thickener comprising 50 partsof 5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea,1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodiumbicarbonate. A cotton fabric is printed with the printing paste thusobtained, and the resulting printed material is dried and steamed insaturated steam at 102° C. for 2 minutes. The printed fabric is thenrinsed, soaped at the boil and rinsed again, if appropriate, and thendried.

What is claimed is:
 1. A dye of the formula (1)

in which Me is Cu or Ni, R₁, is hydrogen or substituted or unsubstitutedC₁-C₄alkyl or R₁, is as defined for A, X₁ is halogen, hydroxyl,C₁-C₄alkoxy, substituted or unsubstituted C₁-C₄alkylthio or amino or isan N-heterocyclic radical which may contain further heteroatoms, u isthe number 1, 2, 3 or 4, q is the number 0 or 1, the benzene rings I, IIor III are unsubstituted or further substituted and A is a radical ofthe formula (2a), (2b) or (3)

in which B₁ and B₂ independently of one another are an aliphatic bridgemember, D₁ and D₂ independently of one another are the radical of adiazo component of the benzene or naphthalene series, R₂ is hydrogen orsubstituted or unsubstituted C₁-C₄alkyl, R₃ and R₆ independently of oneanother are hydrogen, cyano, carbamoyl or sulfomethyl, R₄ is hydrogen,C₁-C₄alkyl or amino, R₅ is amino or N-mono- or N,N- di- C₁-C₄alkylaminowhich are unsubstituted or substituted in the alkyl part and R₇ ishydrogen or C₁-C₄alkyl.
 2. A dye according to claim 1, wherein Me is Cu.3. A dye according to claim 1, wherein R₁ is hydrogen, C₁-C₄alkyl whichis unsubstituted or substituted by hydroxyl or a radical A.
 4. A dyeaccording to claim 1, wherein R₁ is hydrogen or a radical A.
 5. A dyeaccording to claim 1, wherein X₁ is chlorine or fluorine.
 6. A dyeaccording to claim 1, wherein q is the number
 1. 7. A dye according toclaim 1, wherein B₁ and B₂ independently of one another arestraight-chain or branched C₂-C₆alkylene.
 8. A dye according to claim 1,wherein the radicals D₁ and D₂ independently of one another are each aradical of the formula (9a), (9b), (9c), (9d), (9e) or (9f)

 in which (R₁₅)₀₋₂ and (R₁₆)₀₋₂ independently of one another are 0 to 2identical or different s chosen from the group consisting of halogen,C₁-C₄alkyl, C₁-C₄alkoxy and sulfo, Y is vinyl, β-chloroethyl orβ-sulfatoethyl, Y₁ is a group —CH(Br)—CH₂—Br or —C(Br)═CH₂ and l and mindependently of one another are the number 2 or
 3. 9. A dye accordingto claim 1, wherein the formazan radical in the dye of the formula (1)is a radical of the formula (11) or (12)


10. A dye according to claim 8, which has the formula (1a)

in which X₁ is fluorine or chlorine, R₁ is hydrogen or R₁ is as definedfor A and A is a radical of the formula (2a′), (2b′) or (3a)

in which B₁ and B₂ are straight-chain or branched C₂-C₆alkylene, D₁ andD₂ independently of one another are each a radical of the formula (9a),(9b), (9c), (9d), (9e) or (9f), R₅ is amino or N-β-hydroxyethylamino andR₆ is carbamoyl or sulfomethyl.
 11. A process for the preparation of adye according to claim 1, which comprises reacting in each case about 1molar equivalent of a compound of the formula (13)

a compound of the formula (14)

an amine of the formula (15)

with one another in any sequence, where A, Me, R₁, u and q are asdefined in claim 1 and X is halogen.
 12. A process for dyeing orprinting a fibre material containing hydroxyl groups or nitrogen, whichcomprises applying to said fibre material a dye of formula (1) accordingto claim
 1. 13. A process according to claim 12, wherein said fibrematerial is cellulosic fibre material.
 14. A process according to claim12, wherein said fibre material is cotton.